Catalyst-Free Generation of Acyl Radicals Induced by Visible Light in Water to Construct C-N Bonds

2021 ◽  
Author(s):  
Maogang Ran ◽  
Jiaxin He ◽  
Boyu Yan ◽  
Wenbo Liu ◽  
Yi Li ◽  
...  
Keyword(s):  
Visible Light ◽  
Acyl Radical ◽  
Selective Conversion ◽  
Catalyst Free ◽  
Acyl Radicals ◽  
Free Generation ◽  
Direct Generation

We describe herein a catalyst-free and redox-neutral photochemical strategy for the direct generation of acyl radical from α-diketones, and its selective conversion of nitrosoarenes to hydroxyamide or amides with AcOH...

scholarly journals Radical Carbonylative Synthesis of Heterocycles by Visible Light Photoredox Catalysis

Catalysts ◽  
2020 ◽  
Vol 10 (9) ◽  
pp. 1054
Author(s):  
Xiao-Qiang Hu ◽  
Zi-Kui Liu ◽  
Wen-Jing Xiao
Keyword(s):  
Visible Light ◽  
Efficient Synthesis ◽  
Acyl Radical ◽  
Acyl Chlorides ◽  
Aryl Radicals ◽  
Keto Acids ◽  
Acyl Radicals ◽  
Different Types ◽  
The Impact ◽  
Visible Light Photocatalytic

Visible light photocatalytic radical carbonylation has been established as a robust tool for the efficient synthesis of carbonyl-containing compounds. Acyl radicals serve as the key intermediates in these useful transformations and can be generated from the addition of alkyl or aryl radicals to carbon monoxide (CO) or various acyl radical precursors such as aldehydes, carboxylic acids, anhydrides, acyl chlorides or α-keto acids. In this review, we aim to summarize the impact of visible light-induced acyl radical carbonylation reactions on the synthesis of oxygen and nitrogen heterocycles. The discussion is mainly categorized based on different types of acyl radical precursors.

scholarly journals Acyl Radical Chemistry via Visible-Light Photoredox Catalysis

Synthesis ◽  
2018 ◽  
Vol 51 (02) ◽  
pp. 303-333 ◽  
Author(s):  
Ming-Yu Ngai ◽  
Arghya Banerjee ◽  
Zhen Lei
Keyword(s):  
Visible Light ◽  
Carboxylic Acids ◽  
Easy Access ◽  
Hypervalent Iodine ◽  
Photoredox Catalysis ◽  
Acyl Radical ◽  
Diverse Range ◽  
Acyl Chlorides ◽  
Keto Acids ◽  
Acyl Radicals

Visible-light photoredox catalysis enables easy access to acyl radicals under mild reaction conditions. Reactive acyl radicals, generated from various acyl precursors such as aldehydes, α-keto acids, carboxylic acids, anhydrides, acyl thioesters, acyl chlorides, or acyl silanes, can undergo a diverse range of synthetically useful transformations, which were previously difficult or inaccessible. This review summarizes the recent progress on visible-light-driven acyl radical generation using transition-metal photoredox catalysts, metallaphotocatalysts, hypervalent iodine catalysts or organic photocatalysts.1 Introduction2 The Scope of This Review3 Aldehydes as a Source of Acyl Radicals4 α-Keto Acids as a Source of Acyl Radicals5 Carboxylic Acids as a Source of Acyl Radicals6 Anhydrides as a Source of Acyl Radicals7 Acyl Thioesters as a Source of Acyl Radicals8 Acyl Chlorides as a Source of Acyl Radicals9 Acyl Silanes as a Source of Acyl Radicals10 Conclusions and Future Outlook

Generation of Phosphoranyl Radicals via Photoredox Catalysis Enables Voltage–Independent Activation of Strong C–O Bonds

2018 ◽  
Author(s):  
Erin Stache ◽  
Alyssa B. Ertel ◽  
Tomislav Rovis ◽  
Abigail G. Doyle
Keyword(s):  
Carboxylic Acids ◽  
Functional Groups ◽  
Single Step ◽  
Direct Access ◽  
Photoredox Catalysis ◽  
Acyl Radical ◽  
Synthetic Strategy ◽  
Acyl Radicals ◽  
Benzyl Radicals ◽  
Aliphatic Carboxylic Acids

Alcohols and carboxylic acids are ubiquitous functional groups found in organic molecules that could serve as radical precursors, but C–O bonds remain difficult to activate. We report a synthetic strategy for direct access to both alkyl and acyl radicals from these ubiquitous functional groups via photoredox catalysis. This method exploits the unique reactivity of phosphoranyl radicals, generated from a polar/SET crossover between a phosphine radical cation and an oxygen centered nucleophile. We first show the desired reactivity in the reduction of benzylic alcohols to the corresponding benzyl radicals with terminal H-atom trapping to afford the deoxygenated product. Using the same method, we demonstrate access to synthetically versatile acyl radicals which enables the reduction of aromatic and aliphatic carboxylic acids to the corresponding aldehydes with exceptional chemoselectivity. This protocol also transforms carboxylic acids to heterocycles and cyclic ketones via intramolecular acyl radical cyclizations to forge new C–O, C–N and C–C bonds in a single step.

Visible-light-initiated Catalyst-free Oxidative Cleavage of Triaryl-Substituted Alkenes C=C Bonds under Ambient Conditions

2021 ◽  
Author(s):  
Wenjing Li ◽  
Shun Li ◽  
Lihua Luo ◽  
Yichen Ge ◽  
Jiaqi Xu ◽  
...  
Keyword(s):  
Visible Light ◽  
Room Temperature ◽  
Ambient Air ◽  
Oxidative Cleavage ◽  
Ambient Conditions ◽  
Blue Led ◽  
Catalyst Free

The catalyst-free oxidative cleavage of (Z)-triaryl-substituted alkenes bearing pyridyl motif with ambient air under irradiation of blue LED at room temperature has been developed. The reaction was facile and scalable,...

Catalyst-Free [2,3]-Sigmatropic Rearrangement Reactions of Photochemically Generated Ammonium Ylides

Synthesis ◽  
2019 ◽  
Vol 51 (23) ◽  
pp. 4348-4358 ◽  
Author(s):  
Fang Li ◽  
Feifei He ◽  
Rene M. Koenigs
Keyword(s):  
Visible Light ◽  
Sigmatropic Rearrangement ◽  
Tertiary Amines ◽  
Amino Esters ◽  
Catalyst Free ◽  
Rearrangement Reaction ◽  
Rearrangement Reactions ◽  
Free Ammonium

The rearrangement reaction of ammonium ylides furnishes valuable α,α-disubstituted amino esters. In this work, we describe the visible-light photolysis reaction of aryldiazoacetates in the presence of tertiary amines that react via a free ammonium ylide in a sigmatropic rearrangement reaction to provide amino esters in moderate to very good yields (33 examples, up to 97% yield).

Aroyl chlorides as novel acyl radical precursors via visible-light photoredox catalysis

2017 ◽  
Vol 4 (7) ◽  
pp. 1331-1335 ◽  
Author(s):  
Shi-Ming Xu ◽  
Jian-Qiang Chen ◽  
Dan Liu ◽  
Yun Bao ◽  
Yong-Min Liang ◽  
...  
Keyword(s):  
Visible Light ◽  
Visible Light Photocatalysis ◽  
Photoredox Catalysis ◽  
Acyl Radical ◽  
First Time

Abundant and inexpensive aroyl chlorides have been employed for the first time as novel acyl radical precursors in visible-light photocatalysis.

Recent Developments on Catalyst‐Free, Visible‐Light‐Triggered Synthesis of Heterocyclic Scaffolds and Their Mechanistic Study

2021 ◽  
Vol 6 (36) ◽  
pp. 9684-9700
Author(s):  
Munmee Goswami ◽  
Arup Dutta ◽  
Pooja Paul ◽  
Rishanlang Nongkhlaw
Keyword(s):  
Visible Light ◽  
Mechanistic Study ◽  
Catalyst Free ◽  
Recent Developments

scholarly journals Visible Light Promoted, Catalyst‐Free Radical Carbohydroxylation and Carboetherification under Mild Biomimetic Conditions

2020 ◽  
Author(s):  
Lisa‐Marie Altmann ◽  
Viviane Zantop ◽  
Pia Wenisch ◽  
Nina Diesendorf ◽  
Markus R. Heinrich
Keyword(s):  
Free Radical ◽  
Visible Light ◽  
Catalyst Free
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